生物质炭对土壤重金属形态转化及其有效性的影响

为了解土壤重金属形态转化及其有效性对生物质炭修复措施的响应,以Cd、Cu、Pb和Zn复合污染水稻土为供试土样,添加不同粒径(1 mm和0.25 mm)和不同施用量(0、1%和5%)的竹炭(BB)、稻草炭(RSB)进行为期1年的恒温((25±1)℃)培养试验后,检测土壤p H、有效磷含量及重金属DTPA有效态含量的变化,并采用BCR连续浸提法分析生物质炭对土壤中重金属元素化学形态再分配的影响.结果表明:稻草炭的施用显著(p0.05)提高了土壤的p H值,且在RSB-5%(0.25 mm)处理下效果最显著;稻草炭的施用显著(p0.05)提高了土壤的有效磷含量,且5%用量比1%用量效果更明显;而竹炭的施用对土壤p H值和有效磷含量均无显著性影响;RSB-5%(0.25 mm)处理对降低土壤中Cd、Cu、Pb和Zn有效态含量的效果最佳,分别减少了34.5%、50.1%、52.5%和52.1%;在细粒径(0.25 mm)稻草炭处理下,酸溶态Cd和Cu向可还原态和可氧化态转化,酸溶态Zn向可还原态转化;在粗粒径(1 mm)竹炭处理下,酸溶态Cu和Zn向可还原态、可氧化态和残渣态转化;酸溶态Pb在稻草炭处理下向可还原态和可氧化态转化,且细粒径比粗粒径效果更佳;竹炭和稻草炭的施用改变了土壤中上述重金属各形态的分配,且5%用量比1%用量效果更明显.     

Efficient adsorption of Mn(Ⅱ) by layered double hydroxides intercalated with diethylenetriaminepentaacetic acid and the mechanistic study

In this study, greatly enhanced Mn(II) adsorption was achieved by as-synthesized diethylenetriaminepentaacetate acid intercalated Mg/Al layered double hydroxides(LDHsDTPA). The adsorption capacity of LDHs-DTPA was 83.5 mg/g, which is much higher than that of LDHs-EDTA(44.4 mg/g), LDHs-Oxalate(21.6 mg/g) and LDHs(28.8 mg/g). The adsorption data of aqueous Mn(II) using LDHs-DTPA could be well described by the pseudosecond order kinetics and Langmuir isotherm model. Thermodynamics study results also showed that the adsorption process of Mn(II) by LDHs-DTPA was exothermic as indicated by the negative ΔH value. Furthermore, based on the structural, morphological and thermostable features, as well as FT-IR and XPS characterizations of LDHs-DTPA and the pristine LDHs, the adsorption mechanism of Mn(II) was proposed. The carboxyl groups of DTPA were proposed to be the main binding sites for Mn(II), and the hydroxyl groups of LDHs also played a minor role in the adsorption process. Among the three common regeneration reagents, 0.1 mol/L Na_2CO_3 was the best for reusing LDHs-DTPA in Mn(II)adsorption. Besides, the Mn(II) adsorption performance could be hindered in the presence of typical inorganic ions, especially cations. Further specific modifications of LDHs-DTPA are suggested to get more selective adsorption of Mn(II) in practical applications.     

不同修复材料对铅锌尾砂中DTPA浸提态Pb、Zn、Cu、Cd含量的影响

采矿业产生的大量尾砂作为典型的污染源,其含有的重金属等有害成分在雨水浸淋下会直接或间接对周边环境造成污染。为研究尾砂中重金属的污染修复技术,以湖南郴州某废弃矿区的尾砂为研究对象,通过添加质量分数为2.0%的生石灰、还原铁粉、过磷酸钙等廉价修复材料,对尾砂中DTPA浸提态Pb、Zn、Cu、Cd的含量变化进行研究,并就其含量变化所体现的时间效应及机理进行探讨。研究发现,还原铁粉对尾砂的修复作用最好,其次是过磷酸钙。还原铁粉使得尾砂中DTPA浸提态Pb、Zn、Cu、Cd的含量分别降低了59.91%,56.53%,75.81%,35.78%;过磷酸钙使得尾砂DTPA浸提态Pb、Zn、Cu、Cd的含量分别降低了48.85%,44.27%,44.27%,39.23%,可为尾砂中重金属稳定化工程实施提供参考。     

Chemical forms of cobalt and nickel extracted by M1, M3 and CaCl2 DTPA

Mehlich 1(M1), mehlich 3(M3) and CaCl₂ DTPA have been used to predict the available micronutrient in soil. However, the forms of micronutrient extractable by these extractants are not known. In the present study, ten soils, collected from five provinces and the capital of China, representing a wide range of chemical and physical properties, were analyzed by sequential extraction to isolate five forms of cobalt and nickel, they are exchangeable, carbonate bound, Fe Mn oxide bound, organically bound and residual forms. The chemical forms extracted by M1, M3 and CaCl₂ DTPA were also investigated. The results show strong correlation between the carbonate bound or organically bound forms of Co or Ni and the amounts of extractable by any of the above three extractants. The main forms extracted by these extractants are carbonate and organically bound forms. The ranking of these three extractants for extraction of Co and Ni are M1>M3=CaCl₂ DTPA and M1=M3>CaCl₂ DTPA, respectively.     

Cu fractions, mobility and bioavailability in soil-wheat system after Cu-enriched livestock manure applications

Fertilization of crops with livestock manure (LM) is a common waste disposal option, but repeated application of LM containing high concentrations of heavy metals such as Cu could lead to crop toxicity and environmental risk. To examine the Cu availability and uptake by wheat in a Mollisol affected by Cu-enriched LM, pot experiments were conducted. LM (376 mg kg⁻¹ Cu originally) was spiked with different concentrations of Cu (0, 100, 200, 400, 600 and 800 mg kg⁻¹ soil, added as CuSO₄) to simulate soil Cu contamination by LM application. The results indicated that Cu was predominately distributed in organic bound fraction, while the most drastic increase was found in reducible fraction. Acid-extractable fraction played a more important role than other fractions in controlling the mobility and bioavailability of Cu. DTPA-extractable Cu may overestimate the Cu bioavailability since DTPA solution could extract soluble and part of stable forms. The application of LM at 1% level significantly decline the Cu mobility, but that at 3% level exhibited the opposite effect.Although the quantities of Cu in wheat was very low compared with the accumulation in soil, Cu concentrations in roots increased evidently from 12 to 533 mg kg⁻¹ and that in aerial parts were in a narrow range from 12.1 to 32.7 mg kg⁻¹, indicating the more sensitivity of roots to the Cu toxicity. The Cu concentrations in grains after 3% manure application did not approach the threshold for Cu toxicity (<20 mg kg⁻¹) even at higher Cu addition rates.     

Prenatal diagnosis of anatomical connections in conjoined twins by use of contrast magnetic resonance imaging

Omphalopagus conjoined twins were diagnosed by ultrasonography in a pregnant woman at 21 weeks' gestation. In order to clarify the anatomical connections, magnetic resonance imaging (MRI) was performed, having achieved fetal paralysis by intravascular injection of 100 mg of pancuronium into each twin. Prior to MRI, 2 ml of a 0.0001 mmol/ml solution of gadolinium DTPA was also injected into the stomach of one twin. The contrast agent opacified the bowel loops of both twins, indicating bowel to bowel anastomosis. Following pregnancy termination, autopsy confirmed the prenatal diagnosis.     

NTA和DTPA对小麦幼苗对金属吸收的诱导效应

通过盆栽试验和化学提取实验研究了有机配体NTA和DTPA对小麦对沙土中外源重金属Cd,Cu,Pb和Zn的吸收的影响.研究表明,在所试验的土壤金属浓度下,有机配体NTA和DTPA的添加均明显导致小麦幼苗中金属Cu,Zn,Cd和Pb富集量的增加,且DTPA的作用效果高于NTA.10mmol·kg-1DTPA作用效果高于5mmol·kg-1DTPA,但提高程度有限.NTA处理组各金属14 d茎叶富集系数高于7 d茎叶富集系数.对于不同金属,DTPA的作用导致小麦幼苗茎叶富集系数随时间变化的规律不同.5mmol·kg-1NTA,5mmol·kg-1DTPA和10mmol·kg-1DTPA的添加明显导致土壤中4种外源金属的0.01 mol·L-1CaCl2提取态含量的增加.小麦茎叶重金属富集量与0.01mol·L-1CaCl2提取态金属含量具有较好的相关性,说明配体NTA和DTPA的添加导致小麦幼苗对4种金属的富集量的增加是与其导致0.01 mol·L-1CaCl2提取态含量的增加是密切相关的.     

Chemical forms of cobalt and nickel extracted by M1,M3 and CaCl_2-DTPA

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Growth and metal accumulation response of <Emphasis Type="Italic">Vigna radiata</Emphasis> L. var PDM 54 (mung bean) grown on fly ash-amended soil: effect on dietary intake

Plants of Vigna radiata L. var. PDM 54 (mung bean) were grown in soil amended with different amounts (10 and 25%) of fly ash (FA). Although total metal content increased with increasing FA amendment, DTPA-extractable metals were higher for 10% FA. Accumulation of metals by the plants increased with increasing FA amendment and was greater in shoots than in roots (except for Mn and Cu) and seeds (except Mn). The total daily intake (TDI) of all the tested metals in seeds was within the recommended dietary allowance (RDA)/provisional tolerable daily intake (PTDI) for adults, except for Cd, which was higher than recommended values. Principal-components analysis (PCA) based on studies of physicochemical properties, DTPA-extractable metals, and metal accumulation in the different parts of V. radiata showed that physicochemical properties such as cation-exchange capacity, organic carbon, and organic matter had significant positive effects on accumulation of Cd, Co, Ni, and Pb by the plant, whereas EC had a significant negative effect. Although addition of fly ash (10%) initially increased the rate of growth, toxic symptoms were observed for 25% FA. Results from analysis of antioxidants (carotenoids, ascorbic acid, non-protein thiol, and free proline) revealed that these increased more in plants grown in 10% FA than in those grown in garden soil. Cysteine and malondialdehyde (MDA) content increased with increasing FA amendment. PCA also showed that all the antioxidants studied behaved similarly except cysteine, for which there was a close relationship with MDA content. Thus, the results obtained during this study revealed that V. radiata L. var. PDM 54 may be grown in 10% FA and/or contaminated agricultural soil.     

Complexing agents in waste waters of finnish electrolytic and chemical surface treatment plants

Goal, Scope and Background  Complexing agents are one of the major environmental concerns in electrolytic and chemical surface treatment (ECST) industry; e.g. the EU reference document on the best available technology (BREF) pays special attention to the usage of EDTA. However, no comprehensive studies are available on usage of EDTA or other complexing agents or their load to the receiving waters from ECST industry. In this study, the concentrations of complexing agents were analyzed to get an overview of their usage and load and also to recognize their relevance in the environmental permitting and compliance monitoring of such facilities. Methods  Complexing agent concentrations of treated waste water samples of 23 ECST plants with vat volume exceeding 30 m³ was studied. HPLC and GC-MS were used to analyze and identify complexing agent concentrations, ICP-AES to analyze metals, and TOC to analyse the organic load. The number of the plants in this study equals around 50% of such installations in Finland subject to environmental permit as the IPPC directive provides. Results  EDTA, DTPA, and NTA were found in 11 samples out of 23 mainly in rather small concentrations. Their annual load to the receiving waters may be estimated to be 0.3 tons and the total load from Finnish ECST industry can be extrapolated to be up to 1 ton. Compared to the estimated use of 5–10 tons in the industry this finding is rather low, even though in Finland cast-off treatment baths are typically delivered to the hazardous waste treatment plants. Discussion  Since the load of complexing agents is rather low, the chemical waste water treatment seems to be either capable of reducing complexing agent concentrations to some extent or their usage is lower than expected. On the other hand, it is possible that not all complexing agents were identified from the samples. The metal concentrations and TOC were well hand in hand with concentrations found in the Finnish environmental database, which proves that the samples were of average quality of the waste water from the facilities. Conclusions  According to the results, complexing agents cannot be considered as an environmental risk in the ECST industry in Finland; EDTA concentrations are clearly below PNEC_aqua (2.2 mg/l) and the total discharge is very marginal compared to the discharge from the pulp and paper industry. However, DPTA seems to be as commonly used as EDTA, but also biodegradable NTA was found. Recommendations and Perspectives  Since EDTA has gained plenty of attention in the BREF, DTPA and other, poorly biodegradable complexing agents should also be taken into account when the BREF is updated within a few years. Also an EU risk assessment report especially for DTPA should be supplied, since its use is obviously increasing.